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MERIDIAN JUNIOR COLLEGE Calculator Model / No.

JC2 Preliminary Examination
Higher 1
_______________________________________________________________________________

Chemistry 8873/02
Paper 2 13 September 2018
2 hours
Additional Material: Data Booklet
_______________________________________________________________________________

READ THESE INSTRUCTIONS FIRST Examiner’s Use

Write your name, class and register number in the
spaces at the top of this page. MCQ / 30
Paper 1
This booklet contains Section A and Section B. / 33 %

Section A (60 marks) : Page 2 to 15

Q1 / 15
Answer all questions in the spaces provided. You are
advised to spend about 1 h 30 min on Section A.
Q2 / 17
Section B (20 marks): Page 16 to 24 Paper 2
Section A
Answer one question in Section B in the spaces Q3 / 16
provided. You are advised to spend about 30 min on
Section B.
Q4 / 12

INFORMATION FOR CANDIDATES Paper 2

/ 20
Section B
The number of marks is given in brackets [ ] at the
/ 80
end of each question or part question. Paper 2
Total
/ 67 %

Grand Total / 100 %

Grade

_________________________________________________________________________

This document consists of 24 printed pages.

MJC Prelim 2018 8873/02

 2

Section A
Answer all questions in this section, in the spaces provided.

1 Chemists have long studied the trend of elements, and the Periodic Table was celebrated as
an effective way to arrange the elements while reflecting some of the most well-known trends
in their physical and chemical properties.

(a) Using structure and bonding, describe and explain the variation in melting points for elements
aluminium to phosphorous.
[4]
The melting point increases from aluminium (Al) to silicon (Si), then decrease to phosphorous
(P4)

Aluminium: giant metallic lattice structure

Large amount of energy needed to overcome strong electrostatic forces of attraction between
the cations and the sea of delocalised electrons.

Silicon: giant molecular structure

Larger amount of energy to overcome the strong and extensive covalent bonds between Si
atoms in the giant 3–dimensional molecular structure.

Phosphorous: simple molecular structure

Small amount of energy to overcome the weak intermolecular instantaneous dipole–induced
dipole forces of attraction between P4 molecules.

(b) (i) The ionisation energies of Period 3 elements from sodium to argon generally increases,
with the exception of two decreases: from Mg to Al, and from P to S.

Explain these two anomalies in the trend.

[2]
From Mg to Al
Al has a lower 1st I.E as compared to Mg. The 3p electron in Al is further away from the
nucleus compared to 3s electron in Mg. Hence, the 3p electron in Al experience weaker
electrostatic attraction with the nucleus and hence require less energy to remove.

From P to S.
S has a lower 1st I.E as compared to P. Inter–electron repulsion is present in the doubly–
filled 3p orbital of S atom. Hence, it is easier to remove the valence electron in the doubly-
filled 3p orbital of S atom.

MJC Prelim 2018 8873/02

 3

(ii) An element from Period 3 was found to have the following successive ionisation energy
values. Deduce the identity of this element.

Ionisation
1st 2nd 3rd 4th 5th 6th 7th 8th
Energy
Value /
790 1600 3200 4400 16000 20000 24000 29000
kJ mol−1

[1]
The element is silicon because there was a large increase from 4th to 5th ionisation energy.
This indicates that the removal of the 5th electron was from the inner quantum shell and
the element has 4 valence electrons.

(c) Chlorides of Period 3 elements display a wide range of properties.

(i) The pH of the resultant solution when Period 3 chlorides dissolves in or react with water
shows a periodic trend. Sketch the pH trend from NaCl to PCl5.
[1]
pH
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
NaCl MgCl2 AlCl3 SiCl4 PCl5

(ii) Write an equation for the reaction of PCl5 with water.

[1]
PCl5 + 4H2O ⎯⎯
→ H3PO4 + 5HCl

(iii) One of the Period 3 chlorides and BeCl2 have similar reaction with water. Identify this
Period 3 chloride and explain why these two chlorides have similar chemical reactivity.
[1]
Period 3 chloride: AlCl3
Be2+ and Al3+ have similar charge density
OR Be and Al have same atomic radius and electronegativity.

MJC Prelim 2018 8873/02 [Turn Over

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(d) Describe and explain the relative reactivity of elements of Group 17 as oxidising agents.
[2]
Down the group,
• atomic radius increases.
• tendency for X2 to accept electrons decreases.
• tendency for X2 to be reduced to X− decreases.
• oxidising power of X2 decreases.

(e) At the nanoscale, new properties may emerge in certain compounds.

For example, graphene is known to have very high tensile strength and high electrical
conductivity. Describe the structure of graphene and explain how its structure relates to these
two properties.
[3]
Graphene is a single layer of carbon atoms arranged in hexagons as they are in graphite (or a
single layer of graphite). Each carbon atom in the layer is covalently bonded with 3 other carbon
atoms resulting in a hexagonal lattice structure. Graphene has high tensile strength because
of the strong covalent bonds between carbon atoms.

Each carbon atom has a 2p orbital that has a single electron that is not involved in bonding.
This p orbital overlap sideways with its neighbouring carbon atom, resulting in an extended π-
electron cloud of delocalised electrons above and below the plane. Graphene is an excellent
conductor of electricity because it has delocalised mobile electrons over the layer which serves
as charge carriers and can carry an electric current.

[Total: 15]

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2(a) Nearly all petrol and diesel vehicles have some kind of catalytic converter fitted to the exhaust
to reduce the amount of pollutants emitted into the environment. The catalytic converter usually
contains palladium nanoparticles which act as catalyst.

(i) Define the term nanoparticles.

[1]
Nanoparticles are defined as particles with all dimensions between 1–100 nm on the
nanoscale.

(ii) Explain why palladium used is in the form of nanoparticles instead of its bulk form.
[2]
Nanoparticles has high surface area per unit volume, i.e. the proportion of atoms on the
surface of the nanoparticles is larger. As reaction occur on the surface of materials,
chemical reaction often proceed more quickly OR rate of reaction increases.

(iii) The palladium catalyst helps to remove carbon monoxide from the exhaust.
For example,
1
CO + O2 ⎯⎯
→ CO2
2

State the type of catalyst and outline the mode of action of catalyst in this reaction.
[2]
Heterogeneous catalyst

Adsorption: Reactant molecules are adsorbed onto the nanoparticle catalyst surface
through the formation of temporary bonds.

Activation: This adsorption increases the surface concentration of the reactants and
weakens the covalent bonds within the reactant molecules, thereby lowering the activation
energy. Reactant molecules are brought closer together and reaction can take place
between the reactants molecules more easily.

Desorption: Products diffuse away formed from the surface of the catalyst

(b) Carbon monoxide, water and propene can be used to produce butanoic acid according to the
following equation:

metal catalyst
CO + H2O + CH3CH=CH2 CH3CH2CH2CO2H

Draw the structure of the product formed when 2-methylpropene is used in the above reaction.
[1]
CO + H2O + (CH3)2C=CH2 ⎯⎯
→ (CH3)2CHCH2CO2H [1]

MJC Prelim 2018 8873/02 [Turn Over

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(c) Propene can be converted to propanone by the following route.

I II III
CH3CH=CH2 CH3CHClCH3 CH3CH(OH)CH3 CH3COCH3

(i) Suggest the types of reaction for steps I and III.

[2]
step I step III

type of reaction addition oxidation

(ii) State the reagent and conditions for step II.

[1]
aqueous NaOH, heat

(iii) State and explain how the rate of reaction for step II changes when 2-chloropropane is
replaced by 2-iodopropae.
[2]
Relative reactivity of halogenoalkanes depends on the C-X bond strength.
C−I covalent bond is weaker than C−Cl
Relative ease of breaking C−I bond is greater than C−Cl
Hence rate of reaction increases when 2-chloropropane is replaced by 2-iodopropane.

(d) The kinetics of the acid-catalysed reaction of propanone with iodine

H+(aq)
CH3COCH3(aq) + I2(aq) CH2ICOCH3(aq) + HI (aq)

can be investigated experimentally by varying the concentrations of the three substances

involved and determining the time for the colour of the iodine to disappear.

In this method the rate of the reaction is measured in terms of the rate at which the iodine
changes, i.e.
volume of aqueous iodine used
rate ∝
time for the colour of iodine to disappear

The following results were obtained in such an investigation.

Volume of Volume Volume Relative time for the

Volume
Expt CH3COCH3 of H+ /
of I2 / cm3
/ cm3 cm3
1 8 4 8
2 8 4 4
3 4 4 8
4 8 2 8
of H2O / colour of iodine to
cm3 disappear
0 1
4 2
4 2
2 0.5

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 7

(i) Deduce the order of reaction with respect to propanone, iodine and hydrogen ions.
[3]
propanone
Comparing experiment 1 and 3, when conc. of propanone is halved while keeping the
conc. of other reactants constant, rate is halved. Hence order of reaction w.r.t. propanone
is 1

iodine
Comparing experiment 1 and 4, when conc. of iodine is halved while keeping the conc. of
other reactants constant, rate does not change. Hence order of reaction w.r.t. iodine is 0.

hydrogen ions
Comparing experiment 1 and 2, when conc. of H+ is halved while keeping the conc. of
other reactants constant, rate is halved. Hence order of reaction w.r.t. H+ is 1.

(ii) Hence write the rate equation for this reaction.

[1]
rate = k [CH3COCH3] [H+]

(iii) Another experiment, with 0.80 mol dm−3 propanone, 0.0010 mol dm−3 iodine and
0.20 mol dm−3 hydrochloric acid, is carried out at the same temperature.

Calculate the value of the rate constant if the rate is 4.2 × 10−6 mol dm−3 s−1. Give the units
of the rate constant.
[2]
−6
4.2 × 10 = k(0.80)(0.2)
k = 2.6 × 10−5 units: mol−1 dm3 s−1
[Total: 17]

MJC Prelim 2018 8873/02 [Turn Over

3(a) Limited scientific evidence suggests that eating two tablespoons of olive oil daily may reduce
the risk of coronary heart disease. Olive oil comprises mainly of the mixed triglyceride esters of
oleic acid, palmitic acid and other fatty acids. The general chemical structure of olive oil is shown
below where R1, R2 and R3 are alkyl groups or alkenyl groups.

Olive oil undergoes rancidification when exposed to moisture, resulting in an unpleasant taste
and odour. The products formed in the reaction are propane-1,2,3-triol and fatty acids.

Complete the equation to illustrate the rancidification reaction of olive oil.

[2]

OH
HO
+ 3H2O ⎯⎯
→ R COOH + R COOH + R COOH +
1 2 3

OH

(b) Oleic acid has the structure shown.

CH3(CH2)7CH=CH(CH2)7COOH

(i) Describe the bonding in C=C in terms of orbital overlap. Draw a diagram to illustrate your
answer.
[2]

The C=C double bond consists of 1 σ bond and 1 π bond.

The C−C σ bond is formed by the head-on overlap between one orbital of the carbon
atom and one orbital of another carbon atom.

The C−C π bond is formed by the sideway overlap between the 2p orbital of the carbon
atom and 2p orbital of another carbon atom.

MJC Prelim 2018 8873/02

 (ii) Oleic acid exists as a pair of isomers.

Draw and label the structural formulae of the two isomers.

[2]

(CH2)7CH3 (CH2) 7COOH H (CH2)7COOH

C C C C

H H (CH2)7CH3 H

cis isomer trans isomer

(iii) Describe a chemical test that would distinguish oleic acid from ethanoic acid.
[2]
Add Br2 in CCl4 to each compound in the dark at r.t.p.
Oleic acid: Orange-red bromine solution is decolourised.
Ethanoic acid: Orange-red bromine solution is NOT decolourised.

(c) Fig. 3.1 shows a bomb calorimeter, inside a controlled temperature water jacket, which is used
to find an accurate value of standard enthalpy change of combustion of oleic acid.

Fig. 3.1

(i) What is meant by the standard enthalpy change of combustion of oleic acid?
[1]
It is the energy released when 1 mole of oleic acid is completely burned in (excess) oxygen
under standard conditions (298 k and 1 bar).

(ii) Explain why the steel ‘bomb’ is flushed with a high pressure of oxygen at the start of the
experiment.
[1]
It is to ensure that there is sufficient O2 present in the steel bomb for complete combustion.

MJC Prelim 2018 8873/02

 10

(iii) There is no heat lost from the calorimeter because of the controlled temperature water
jacket. Suggest how the controlled temperature water jacket achieves this.
[1]
The temperature of water in the jacket is raised with an electric heater so that it just
matches the average temperature of the calorimeter.

(iv) A 2.98 g sample of oleic acid (C18H34O2) is burned in a bomb calorimeter with a heat
capacity of 1.98 kJ K−1. The temperature of the calorimeter increases by 59.3 oC.

Calculate the standard enthalpy change of combustion of oleic acid.

[2]
Heat absorbed by calorimeter = 1.98 × 59.3 = 117 kJ
2.98
Amount of oleic acid used = = 0.0106 mol
282.0
117
ΔHco(oleic acid) = − = − 11000 kJ mol−1
0.0106

(v) Use the bond energies given in the Data Booklet to calculate another value for the
standard enthalpy change of combustion of oleic acid.

H H H H H H H H H
H H H H H H H H
C C C C C C C C C O
H C C C C C C C C C
H H H H H H H
H H H H H H H H
OH
oleic acid

You may find the following information useful in your calculation.

An oleic acid (C18H34O2) molecule contains 33 C−H bonds,16 C−C bonds and other bonds.
[3]
51
C18H34O2 (l) + O2 (g) → 18 CO2 (g) + 17 H2O (l)
2
Bond breaking (endothermic) Bonds forming (exothermic
 energy absorbed  energy released
33 C-H bonds 33 (410) 36 C=O bonds 36 (805)
in CO2
16 C-C bonds 16 (350) 34 O-H bonds 34 (460)
1 C=C bond 610
1 C=O bond 740
1 C-O bond 360
1 O-H bond 460
51 51
O=O bonds (496)
2 2
Total 33948 kJ mol-1 Total 44620 kJ mol-1

ΔHco(oleic acid) = 33948 − 44620 = − 10672 = − 10700 kJ mol−1

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 11

(vi) Suggest a reason for the discrepancy between the value in (c)(iv) and that in
(c)(v).
[1]
Bond energy values of polyatomic molecules in the Data Booklet are average values.
OR
Oleic acid is not in gaseous state.
[Total: 16]

MJC Prelim 2018 8873/02 [Turn Over

4(a) There are two types of polymerisation, addition and condensation

Account for the differences between these two types of polymerisation.

[2]

Addition Polymerisation Condensation Polymerisation

Involves monomers containing Involves monomers containing

Type of
double or triple bonds alcohol, carboxylic acid or amino
monomers
(unsaturated compounds) (–NH2) functional groups.

By-products
No loss of molecules and the Involves elimination of small
during
polymer is the only product. molecules e.g. H2O or HCl.
polymerisation

Empirical
formula of Addition polymers have the Empirical formula of the
polymer as same empirical formula as their condensation polymer is not the
compared to monomers. same as that of the monomer.
its monomers

(b) Super-absorbent polymers have the ability to absorb 200 – 300 times their own mass of water.
They are classified as hydrogels and are widely used in personal disposable hygiene products
such as diapers. However, these synthetically made hydrogels are usually non-biodegradable.

The diagram below shows part of the structure of a hydrogel.

HO O
C

CH2 CH CH2 CH

C cross-link
O
O
CH2
HO CH2 C CH2 OH

CH2

O
O
C

CH2 CH CH2 CH

C
HO O

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 13

The hydrogel is formed from chains of one polymer which are then cross-linked using another
molecule.

(i) State the type of polymerisation used to form these polymer chains.
[1]
Addition polymerisation

(ii) Draw the displayed structural formula of the monomer used.

[1]
H O O
O C H Cl C H
C C C C
H H OR H H

(iii) Draw the structure of the molecule used to cross-link the polymer chains.
[1]
OH
CH2
HO CH2 C CH2 OH
CH2
OH

(iv) Once a hydrogel has absorbed water, it can be dried and re-used many times. Explain
why this is possible, referring to the structure.
[1]
Water is held to the hydrogel by hydrogen bonds formed between water molecules and –
COOH of the chain or –OH of the cross-link. These hydrogen bonds can be easily broken
to release the held water molecules during drying.

(v) The amount of cross-linking has little effect on the ability of the gel to absorb water.
Suggest why this is the case.
[1]
The amount of cross-linking does not affect the number of O-H groups available for
hydrogen bonding.

(v) Suggest one property of the hydrogel that will change if more cross-linking takes place.
Explain how the increased cross-linking brings about this change.
[2]
Hydrogel becomes harder / more rigid / less flexible / more brittle.

The strong cross-link covalent bonds between chains cannot be easily overcome. More
cross–links hold the chains more tightly and strongly OR decreases the freedom of
movement of individual chains

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 14

(c) Unlike hydrogel, the polymer, ‘polyactide’ or PLA is biodegradable. The monomer required to
produce PLA is lactic acid, 2-hydroxypropanoic acid.

The structure of lactic acid is as shown.

H

HO C COOH

CH3

(i) Draw the structure of the polymer PLA, showing two repeat units.
[1]
O
O
O
O n

One of the reasons PLA has attracted so much attention is that it is biodegradable. This does,
however restrict some potential uses. The polymer has a melting point of around 175 °C , but
soften between 60 – 80°C. However, its properties enable it to have a range of uses in food
packaging and in fibres.

(ii) Explain why PLA would not be a suitable packaging materials for food pickled in vinegar.
[1]
PLA contains ester linkages in the polymer which can be hydrolysed by the acid present
in vinegar e.g. CH3COOH (aq), under prolonged exposure.

(iii) Suggest why PLA containers are not usually used to hold hot drinks.
[1]
PLA is a thermoplastic polymer. PLA softens when heated and hence the PLA container
changes shape easily as weak van der Waals’ forces of attractions between chains are
easily overcome and the chains are able to slide past each other.

[Total: 12]

END OF SECTION A

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 15

Section B
Answer one question from this section, in the spaces provided.

5(a) Three natural–occurring compounds used commercially are shown below:

CH3
H
H3C CH3
C O

OH
OH
C
H3C CH3 C
CH3 H3C CH2
CH3

2 methylpropan–2–ol Menthol Carvone

(i) Describe a set of two chemical tests that can be used to distinguish the above three
compounds. Write an equation for each reaction that takes place.
[5]
Test: Add K2Cr2O7 (aq), H2SO4 (aq) to each compound separately and heat.

Observations:
• 2 methylpropan–2–ol: Orange acidified K2Cr2O7 remains.
• Menthol : Orange acidified K2Cr2O7 turns green.
• Carvone: Orange acidified K2Cr2O7 remains.
H
H3C CH3 H
C H3C CH3
C
K2Cr2O7 (aq / dilute H2SO4
OH + [O] + H2O
O

CH3
CH3

Test: Add Br2 (CCl4) / Br2 (aq) to remaining compounds in the dark separately at r.t.p.

Observations:
• 2 methylpropan–2–ol: No decolourisation of orange–red Br2 (CCl4)
• Carvone: Decolourisation of orange–red Br2(CCl4)
CH3 CH3
Br
O Br O
+ 2Br2

Br
C C
H3C CH2 H3C CH2Br

MJC Prelim 2018 8873/02 [Turn Over

 16

(ii) Carvone can be converted to organic compound D in two steps.

CH3 O
CH3
O
O

C
H3C CH2 C
H3C CH2

Carvone Compound D

State the reagents and conditions necessary for each step. Give the structure of the
intermediate involved in the conversion.
[3]

CH3 O
CH3
O
O

C
H3C CH2 C
H3C CH2

LiAlH4 in dry ether, r.t.p.

OR CH3CH2COOH, conc. H2SO4, heat
CH3
NaBH4 in ethanol, r.t.p.
OH

C
H3C CH2

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 17

(b) Ammonia was used in smelling salts to treat fainting. Modern smelling salt solution may contain
other products such as lavender oil to act in conjunction with aqueous ammonia.

When 40 cm3 of aqueous ammonia was titrated against 0.200 mol dm–3 sulfuric acid, H2SO4
using a pH meter, the following graph was obtained.

2NH3 (aq) + H2SO4 (aq) ⎯ ⎯

→ (NH4)2SO4 (aq)

pH

Volume of H2SO4
added / cm3
0 10.0 20.0

The base dissociation constant for ammonia, Kb is 1.78 x 10–5 mol dm–3.

(i) Explain what is meant by the terms Bronsted–Lowry base and conjugate acid–base pair.
Illustrate your explanation using ammonia in the above reaction with sulfuric acid.

Explain why the Arrhenius definition of base does not apply for ammonia in the above
reaction.
[3]
A Bronsted–Lowry base is a proton acceptor.
A conjugate acid–base pair is a pair of species that differs from each other by a proton.

NH3 (aq) + H+ (aq) ⎯⎯

→ NH4+ (aq)
proton acceptor proton from H2SO4
base conjugate acid

An Arrhenius base is a substance that has OH in its formula and releases OH– when
dissolved in water. This definition does not explain basic property of ammonia that does
not contain the OH group.

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 18

(ii) Write an expression for the base dissociation constant, Kb, of ammonia.
[1]
+ −
[NH4 ][OH ]
NH3 + H2O NH4+ + OH– Kb =
[NH3 ]

(iii) Using the titration curve provided, state the volume of sulfuric acid needed for the exact
neutralisation of 40 cm3 of aqueous ammonia. Calculate the initial concentration of
aqueous ammonia.
[2]

From the graph, the equivalence volume is 10.0 cm3.

10
Amount of H2SO4 in 10.0 cm3 = × 0.200 = 0.00200 mol
1000

Mole ratio: 2NH3 ≡ H2SO4

Amount of NH3 in 40.0 cm3 solution = 0.00400 mol
0.00400
Initial concentration of ammonia in 40.0 cm3 = = 0.100 mol dm–3
 40.0 
 
 1000 

(iv) The resultant solution at the end of the titration can be considered as a sulfuric acid
solution of concentration 0.0333 mol dm–3. Calculate the pH of this resultant solution to
2 decimal place.
[1]
[H2SO4] = 0.0333 mol dm–3

Since H2SO4 is a strong diprotic acid,

[H+] = 2 x 0.0333 = 0.0666 mol dm–3

pH = - lg [H+] = - lg (0.0666) = 1.18 (2 d.p.)

(v) Suggest an appropriate indicator for the titration, giving a reason for your choice.
[1]
Methyl orange / methyl red may be used for this strong acid–weak base titration.

The pH transition range of the indicator (around 3.0 – 4.5) lies within the region of the
rapid pH change (around 3 – 7) over the equivalence point.

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(vi) Explain what do you understand by the term buffer solution.

[1]

A buffer solution is one which is capable of maintaining a fairly constant pH when small
amounts of acid or base are added to it.

(vii) The Henderson–Hasselbalch equation is useful for the estimation of the pH of a buffer
solution.

An alternative form of the equation is shown below which can be used to determine the
pOH of a basic buffer solution.
BH+ 
pOH = pKb + log10
[B]
Calculate the pH of a basic buffer solution, if the solution contains NH4+ and NH3 in a
2 : 1 ratio. given that the base dissociation constant, Kb of ammonia, NH3 is
1.78 x 10–5 mol dm–3.
[2]
NH4+ 
pOH = pKb + log10
[NH3 ]
2
pOH = – log (1.78 x 10–5) + log10  
 1
pOH = 5.05

pOH = 14 – pH = 14 – 5.05
= 8.95

(viii) The enthalpy changes of neutralisation involving sulfuric acid with two bases are shown
below.

sodium hydroxide, NaOH – 57.3 kJ mol–1

ethylamine, CH3CH2NH2 – 51.5 kJ mol–1

Comment and explain for the above observation as fully as you can.
[1]
Ethylamine is a weak base. CH3CH2NH2 is only slightly dissociated in aqueous solution.

CH3CH2NH2 + H2O ‡ˆ ˆ †ˆˆ CH3CH2NH3+ + OH–

Some of the energy evolved from the neutralisation process is used to further dissociate
the weak base completely.

Hence, the enthalpy change of neutralisation involving CH3CH2NH2 is less exothermic.

[Total: 20]

MJC Prelim 2018 8873/02 [Turn Over

6(a) Hydroxylamine, NH2OH is commonly used in photography developing solution. Prolonged
exposure to hydroxylamine by photography developers might cause irritation to their respiratory
tract. To minimise the health hazard on these developers, the safety limit of the concentration
of hydroxylamine is capped at below 0.00200 mol dm–3.

A scientist performed the following experiment to determine if a sample of photography

developing solution was within the safety limit.

100 cm3 of NH2OH solution was added to 40 cm3 of 0.015 mol dm-3 acidified I2 (aq) solution.
In this reaction, iodine is used in excess and NH2OH is oxidised to form dinitrogen monoxide,
N2O.

(i) Using half-equations, write a balanced equation for the reaction between NH2OH (aq) and
I2 (aq) in an acidic medium.
[2]

Reduction: I2 + 2e ⎯⎯→ 2 I–

Oxidation: 2 NH2OH ⎯⎯→ N2O + H2O + 4H+ + 4e

Overall: 2NH2OH + 2I2 ⎯⎯→ N2O + H2O + 4I– + 4H+

A 25.0 cm3 aliquot of the resultant reaction mixture was then titrated with a standard solution of
0.00500 mol dm–3 sodium thiosulfate, Na2S2O3 (aq).

I2 (aq) + 2 S2O32– (aq) ⎯⎯

→ 2I− (aq) + S4O62– (aq)

Starch solution was added as indicator for this titration to enhance the contrast of the colour
change at the end-point of the titration. 22.50 cm3 of Na2S2O3 (aq) was required.

(ii) State the expected colour change at the end-point of the titration.
[1]
Blue-black to colourless.

(iii) Calculate the amount of I2 remaining in the reaction mixture.

[2]
22.50
Amount of Na2S2O3 required = ×0.00500 = 1.125 x 10−4 mol
1000
2S2O32− ≡ I2
1
Amount of I2 remaining in 25 cm3 of the reaction mixture = × 1.125 × 10 −4
2
= 5.625 x 10-5 mol

140
Amount of I2 remaining in reaction mixture (140 cm3) = × 5.625 × 10 −5
25.0
= 3.15 x 10-4 mol

MJC Prelim 2018 8873/02

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(iv) Calculate the concentration of NH2OH in 100 cm3 sample of the photography developing
solution. Hence conclude whether the solution is within the safety limit.
[2]
 40.0 
Amount of I2 reacted with NH2OH =  ×0.015  mol – 3.15 x 10-4 mol
 1000 
= 2.85 x 10-4 mol

NH2OH ≡ I2

Amount of NH2OH present in 100 cm3 = 2.85 x 10-4 mol

[NH2OH] = 2.85 x 10-4 mol / (100/1000) = 0.00285 mol dm-3

Solution is > 0.00200 mol dm-3, hence it is NOT within the safety limit.

(v) Iodate(V) ion, IO3– was used to generate iodine required for the reaction with NH2OH.

In this IO3– ion, the central iodine atom can expand its octet structure. Draw the
dot-and-cross diagram of IO3– ion.

− [1]

xx
x
x
x I x O
O x
O

(vi) From your answer in (a)(v), state the bond angle around the central iodine atom and
account for the shape of IO3– ion.
[2]

IO3– have 3 bond pairs and 1 lone pair around the central I atom.

To minimise repulsion and maximise stability, the 4 electron pairs are directed toward
the corners of a regular tetrahedron.

Lone pair – bond pair repulsion > bond pair – bond pair repulsion

IO3– is trigonal pyramidal, with a bond angle of 107o

MJC Prelim 2018 8873/02 [Turn Over

 22

(b) In an industrial process, 5 mol of dinitrogen tetroxide, N2O4 and 7 mol of nitrogen monoxide, NO
was heated in a 2.0 dm3 vessel. The temperature is kept at 500 °C. The two gases react slowly
to form blue dinitrogen trioxide, N2O3 according to the following equation. It was found that the
equilibrium mixture contains 2.3 mol of NO.

ˆ ˆˆ †ˆ
N2O4 (g) + 2NO (g) ‡ 2N2O3 (g) ΔH = – 30.5 kJmol−1

(i) Write an expression for the equilibrium constant, Kc for the reaction, stating the units.
[1]
2
[N2O3 ]
Kc = 2
mol–1 dm3
[N2O 4 ] [NO]

(ii) Determine the equilibrium concentrations of the three gases. Hence, calculate the value
of Kc.
[2]
N2O4 (g) + 2NO (g) ‡ˆ ˆ †ˆ 2N2O3 (g)
Initial amount / mol 5 7 0
- ½ (4.7) =
Change in amount/ mol - 4.7 +4.7
- 2.35
Equilibrium amount / mol 2.65 2.3 +4.7

[N2O3 ]2
Kc =
[N2O 4 ][NO]2
2
 4.70 
 
Kc =  2.0 
2
 2.65   2.30 
  
 2.0   2.0 

Kc = 3.15 mol-1 dm3

(iii) Predict and explain the effect of increasing temperature on the equilibrium position and
equilibrium composition.
[2]
As temperature increases, the system will try to remove the heat added. By Le Chatelier’s
Principle, the equilibrium position will shift left towards the endothermic reaction to absorb
heat.

The new equilibrium mixture contains less product, N2O3 and more reactants N2O4 and
NO.

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(iv) Sketch on the same axes, how the concentration of the three gases will change when
temperature was increased at t.
[2]
concentration / mol dm-3

N2O3 (g)

− ∆2X

N2O4 (g) +∆X

+∆2x
NO (g)

time / min
t

(v) State the operating pressure and temperature (high or low) required to obtain a high yield
of N2O3. Explain your answer.
[2]
To obtain a high yield of N2O3, a high pressure and low temperature should be used
instead.

At high pressure, the system will try to reduce the pressure

By Le Chatelier’s Principle, the equilibrium position shifts right to decrease the number
of moles of gases to decrease pressure. [N2O3] increases, resulting in a higher yield.

To obtain a high yield of N2O3, a low temperature should be used instead.

At low temperature, the system will try to produce heat. By Le Chatelier’s Principle, the
equilibrium position will shift right towards the exothermic reaction to release heat. [N2O3]
increases, resulting in a higher yield.

(vi) Hence, suggest why the operating temperature is fixed at a moderately high temperature
of 500 °C.
[1]
If the temperature is too low, the rate of reaction will be too slow. Hence, a moderately
high temperature is chosen as a compromise between the conflicting demands of rate
and yield of the reaction.
[Total: 20]

END OF PAPER

MJC Prelim 2018 8873/02 [Turn Over